EP0186925A1 - Verfahren zur biologischen Reinigung von verunreinigten Gasen - Google Patents

Verfahren zur biologischen Reinigung von verunreinigten Gasen Download PDF

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Publication number
EP0186925A1
EP0186925A1 EP85202029A EP85202029A EP0186925A1 EP 0186925 A1 EP0186925 A1 EP 0186925A1 EP 85202029 A EP85202029 A EP 85202029A EP 85202029 A EP85202029 A EP 85202029A EP 0186925 A1 EP0186925 A1 EP 0186925A1
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EP
European Patent Office
Prior art keywords
gas
gases
stage
purification
contaminated
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Application number
EP85202029A
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English (en)
French (fr)
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EP0186925B1 (de
Inventor
Johannes Albertus Don
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Nederlandse Organisatie voor Toegepast Natuurwetenschappelijk Onderzoek TNO
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Priority to AT85202029T priority Critical patent/ATE37172T1/de
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/84—Biological processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel

Definitions

  • the invention relates to a method for the biological purification of contaminated gases containing contaminants which are not or hardly water-soluble by means of one or more types of microorganism.
  • a biofilter may be depicted by Figure 1 in which (1) represents an inlet pipe for contaminated air, (2) a humidifying device for the contaminated air, (3) a spray device, (4) a pipe for the humidified contaminated air, (5) a pressure chamber or gravel bed, (6) a filter bed, for example of compost and/or peat, and (7) - an outlet for the purified air.
  • a biofilter such as Low running costs and a simple construction of the system, this system has a number of disadvantages such as Large dimensions and a Limited surface Loading.
  • biofilters normally have a Large area, for example of 300-1,200 m 2 and a thickness of approximately 0.5-1 metre.
  • the Low surface Loading of a biofiLter is associated with the faLL in pressure through the filter bed which because of energy costs should not be more than 100-200 mm of water column. Because of this the surface Loading of the modern compost filters is approximately 100 m 3 /m 2 /hour. By using compost compounded in a special manner the surface loading can be increased by a factor of 3-5.
  • a device of this type may be represented by Figure 2 in which (8) represents a wash column, (9) an inlet pipe for contaminated air, (10) an outlet pipe for the purified air, (11) a pipe for the water loaded with contaminants, (12) an aeration vessel with an air inlet pipe (13) or outlet pipe (13a) respectively and (14) a pipe for purified water.
  • a system of this type has, however, also disadvantages such as the occurrence of contamination of the packing in the wash column (8) by microorganisms, while at the same time the stability of the microorganisms in a system of this type leaves something to be desired.
  • the wash column (8) employing water only a limited rate of mass transfer is attained for numerous organic compounds such as toluene. Because of this the size of the wash column and also the rate of flow of the washing liquid should be considerable.
  • German Offenlegungsschrift 3,227,375 a method is known for the purification of waste gases containing biologically degradable contaminants, which are slightly water-soluble. These contaminants are absorbed by a suspension of active sludge in water and broken down aerobically by microorganisms in the active sludge present in a vessel. For increasing the absorption capacity or achieving a buffer capacity for peak-loads 0.2 - 10 g of active charcoal per liter is added to the active sludge suspension after which the contaminants absorbed in the sludge or on active charcoal respectively are degraded aerobically.
  • the amount of contaminants to be adsorbed is limited to a maximum of a few grams per liter.
  • the advantages of the system according to the invention comprising the anaerobical purification stage are the smaller sludge production and the decreased need for nutrients in respect to aerobical systems. Further there is hardly any need for energy necessary for stirring etc. in the anaerobical purification of aqueous sludges, this contrary to aerobical systems.
  • a further advantage in a number of cases is the production of methane.
  • Another advantage of the invention is that the large amount of carrier material has a stabilising action on the microorganisms.
  • the open-bed structure of the first stage of the method according to the invention can be constructed in a compact manner from the technical point of view. Because of the low drop in pressure and the rapid mass transfer a surface loading of, for example, 5,000-10,000 m 3 /m 2 /hour can in principle be attained.
  • the second stage of the method according to the invention is a bioreactor in which the suspension loaded with contaminants is purified anaerobically. This stage can be preceded or followed by an aerobical stage. As an example of such a combination an aerobic conversion of NH 3 into N0 3 - and subsequently an anaerobic conversion of the N0 3 - obtained into N 2 may be mentioned.
  • the second stage of the method according to the invention can also be constructed in a compact manner.
  • the percentage of space taken up by air in the device according to the invention is much lower than in a biofilter known from the prior art (a few per cent against 50).
  • the quantity of inert material is small compared with the known biofilters.
  • a smaller floor area can be achieved because a greater installation height is possible.
  • this is not achievable because the pressure drop through the filter rises too high and because of the resuLting energy consumption.
  • the bioLogicaL reactor may be dimensioned twelve times smaller because outside the emission period the compounds stored in the adsorbents can be broken down further.
  • the appliance necessary for the carrying out of the method according to the invention can be constructed from equipment common in the processing industry.
  • the biological purification according to the invention can be fitted into already existing industrial processing systems in a simple manner.
  • the invention has the advantage that specific microorganisms can be used so that it is possible to Load carrier material with the said microorganism or microorganisms which give optimum results for a certain conversion.
  • (in)organic compounds can be used as nutrients for the microorganisms concerned.
  • the method according to the invention can be carried out in a device according to Figure 3.
  • this device represents a wash appliance, (16) an inlet pipe for contaminated air, (17) an outlet pipe for the purified air, (18) an inlet pipe for the suspension of carrier optionaLLy Loaded with a microorganism, (19) an outlet pipe for the suspension of the carrier optionally Loaded with a microorganism, (20) a biological reactor or reactor system and (21) a waste pipe. Via the waste pipe (21) a portion of the Liquid is periodically reLeased in order to prevent poisoning by accumulation of breakdown products.
  • the washappliance(15) can be constructed in the form of, for example, a packed column (for example very open with a/channeL-type packing) or as a turbulence washing device.
  • a packed column for example very open with a/channeL-type packing
  • turbulence washing device for example, a turbulence washing device.
  • the biological reactor (20) it is emphasised that the Latter can be operated both aerobicaLLy and anaerobically, and in addition, if required, may consist of several separate stages for the breakdown of various compounds which takes place under different conditions.
  • FIG. 4 A preferred embodiment of the device shown in Figure 3 is depicted in Figure 4.
  • (22) represents a connecting pipe between reactor (20) and a separating device (23), (24) a return pipe from the separating device (23) to the reactor (20) and (25) a waste pipe.
  • the separating device (23) is, for example, a settling tank or, advantageously, a hydrocyclone (system) from which a carrier optionally Loaded with microorganisms is removed via pipe (18) and fluid with optionally Loose microorganisms via pipe (24).
  • the carrier materials are used, for example, in a quantity of 2-40% referred to the suspension.
  • microorganisms in the method according to the invention are, on the one hand, dependent on the prevailing conditions, i.e. anaerobic or aerobic conditions, and on the other hand, on the desired reaction. More particularly, the following microorganisms may be used under anaerobic conditions:
  • ExampLes of waste gases to be purified are air Loaded with (in)organic contaminants, for example originating from intensive Livestock breeding, and also industrial waste gases which are contaminated, for example, with hydrocarbons such as toluene and the Like.
  • Another example of a gas to be puri fied is fermentation gas which contains, for exampLe, 0.1-2X of H 2 S. On burning an H 2 S-containing fermentation gas of this type corrosion problems, in particular, occur in the combustion equipment.
  • a pH buffer is preferably used.
  • gases which are contaminated with nitrogen-containing compounds are advantageously treated at a pH of 7-9 and gases which contain sulphur-containing contaminants advantageously at a pH of 2-4.
  • microorganisms are sensitive to toxic components in the contaminated gas it is advisable in such a case to subject the gases to be purified to a chemical pretreatment.
  • an excessive concentration of aldehydes may have a toxic effect on the microorganisms so that a mild chemical oxidation of the aldehydes to the corresponding acids is used with advantage.
  • the microorganism used for the purification should, as a rule, be provided with a nutrient such as nitrate.
  • a nitrate addition of this type is used in the anaerobic purification of H 2 S-containing fermentation gas, in which the foLLowing reaction occurs:
  • the Last-named reaction can be carried out by a number of microorganisms such as ThiobaciLLus denitrificans and Thiomicrospira denitrificans.
  • the H 2 SO 4 obtained can be neutralised by means of a base such as MgCO 3 , CaC0 3 or Ca(OH) 2 .
  • the invention reLates to a method for the biological purification of a contaminated gas by means of one or more varieties of microorganism, in which the gas to be purified contains one or more gaseous nitrogen compounds as contaminant.
  • the purification of gases with gaseous nitrogen compounds such as NH 3 in them is known, for example, from intensive Livestock breeding.
  • the said NH 3 can be converted into N0 3 - (nitrate) by means of, for example, biofiLters.
  • the disadvantage of the classical operation is, however, that the N0 3 - is released in Large quantities of water, which water then has to be discharged and therefore causes environmental contamination.
  • the bioLogicaL purification of gases can be carried out in a more efficient manner if the gas to be purified contains at Least one or more NO x gases as contaminant, x having a vaLue of 0.5-2.5. Because of the conversion of the NO x gases into the nitrate, the contaminant NO x can be removed at the same time, for example from flue gases, the waste gases of nitric acid factories or the gases extracted above pickling baths provided with nitric acid.
  • the NO x content of the gases to be purified is, for example, 10-1000 ppm.
  • This Last-named method can be applied by using many types of purification device such as biofilters, bio- washers and devices based on suspensions of carrier material optionally Loaded with microorganisms.
  • the waste water from biofiLters and the Like has a considerable bioLogicaL nutritional value.
  • the quantity of nitrate may rise to 50-100 gram of nitrate/Litre of waste water.
  • the microorganisms present on the carrier material do not die off.
  • the purification method according to the invention based on the use of NO x gases can be used in many fields.
  • the nitrate (N0 3 -) is, as already mentioned, formed from the NO x , which leads, for example, in the case of gases contaminated with hydrocarbons to an increased hydrocarbon consumption or breakdown.
  • a specific application of the Last-named method according to the invention consists in a biological purification system in respect of the purification and combustion of fermentation gas. More particularly, this specific method can be clarified by reference to Figure 5, in which (27) represents an inlet pipe for fermentation gas, (26) a reactor, (28) a pipe for purified fermentation gas, (29) a combustion device for the fermentation gas, (30) a pipe for flue gases, (31) a reactor for the purification of the flue gases, (32) an outlet pipe for the purified flue gases, (33) a pipe for the supply of water, (34) an outlet pipe for the nitrate solution obtained in the second reactor vessel and (35) a waste pipe from the first reactor.
  • the quantity of nitrate formed in reactor (31) can also be controlled by adjustment of the combustion device (29).
  • an anaerobic conversion takes place of the H 2 S present in the fermentation gas according to the reaction below: 8N0 3 - + 5H 2 S H 2 SO 4 + 4N 2 + 4SO 4 2- + 4H 2 0
  • the H 2 S0 4 obtained in this reactor is neutralised with a base such as CaCO 3 or Ca(OH) 2 .
  • the purified fermentation gas originating from the first reactor is subsequently burnt in a combustion device (29). During this combustion flue gases are released which contain NO x . These flue gases, diluted or undiluted, are treated aerobicaLLy in asecond reactor (31), the NO x being converted into N0 3 -(nitrate). Apart from purified flue gases, the nitrate formed is removed from this second reactor (31), which nitrate can be used in the first reactor for the anaerobic conversion of H 2 S which takes place therein.
  • microorganisms which can be used for the anaerobic conversion Of H Z S mention may be made of ThiobaciLLus denitrificans and Thiomicrospira denitrificans.
  • microorganisms which are suitable for the conversion of NO x into N0 3 - mention may be made of varieties of Nitrosomonas.
  • the device according to the invention consisted, as shown in Figure 3, of a wash column (15) having a floor area of 30 m 2 and a height of 1 m. Water containing 15% by weignt of active charcoal was used as suspension. The active charcoal was Loaded with microorganisms by impregnation with percolation water from composted domestic refuse. The Liquid/gas ratio in the wash column (15) was 2 kg/kg. The suspension Loaded with contaminant was then fed to a bioreactor (20) which had a capacity of 60 m 3 (vessel having a base area of 30 m 2 and a height of 2 m). As a result of the biological breakdown occurring in the bioreactor a removal efficiency of 75-95% was obtained.
  • the above device according to the invention occupied a floor area of 30 m 2 and had a height of approx. 5 m.
  • the device according to the invention occupies a considerably smaller floor area (30 m 2 as against approx. 400 m 2 ).
  • the filling material was at the same time buffered to a pH of 7-9 by addition of Lime (CaC0 3 ).
  • the gas contaminated with NO x was passed through with a surface Loading of as much as 400 m 3 /m 2 /hour. Despite this a removal efficiency of 80-95% was nevertheless achieved.
  • a pilot plant biofilter with a tree bark/compost mixture as biologically active filling material was used for the purification of gas which was Loaded with 330 mg of toluene/m 3 .
  • the contaminated gas was passed through with a surface Loading of 300 m 3 /m 2 /hour.
  • the toluene removal efficiency was Less than 10%. However, with an NO x supplementation of 10-20 mg NO x /m 3 the toluene removal efficiency increased to over 90%. On using flue gas as NO x source, only 1-5% of flue gas referred to the toluene-containing gas had to be added to the gas to be purified.
  • the fermentation gas purified in this manner was then fed via pipe (28) to a combustion device (29) and burnt, a flue gas flow of 200 m 3 /hour with an NO x content of 500 ppm being obtained via pipe (30).
  • a second biofiLter (31) This second filter was filled with a tree bark/compost mixture and had a floor area of 2,5 m 2 and a height of 2 m.
  • the waste water from the second biofiLter (31) was periodically sprayed via pipe (34) in a quantity of 50-100 Litre/day over the bed of the first biofilter (26), the nitrate present in the said waste water then being used in the first biofilter as nutrient for the microorganism Thiobacillus denitrificans present therein.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Biomedical Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Molecular Biology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Treating Waste Gases (AREA)
  • Biological Treatment Of Waste Water (AREA)
EP85202029A 1984-12-12 1985-12-06 Verfahren zur biologischen Reinigung von verunreinigten Gasen Expired EP0186925B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT85202029T ATE37172T1 (de) 1984-12-12 1985-12-06 Verfahren zur biologischen reinigung von verunreinigten gasen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
NL8403773A NL8403773A (nl) 1984-12-12 1984-12-12 Werkwijze voor het biologisch reinigen van verontreinigde gassen.
NL8403773 1984-12-12

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EP0186925A1 true EP0186925A1 (de) 1986-07-09
EP0186925B1 EP0186925B1 (de) 1988-09-14

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AT (1) ATE37172T1 (de)
DE (1) DE3564935D1 (de)
NL (1) NL8403773A (de)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218958A2 (de) * 1985-10-15 1987-04-22 Combustion Engineering, Inc. Mikrobiologische Entschwefelung von Gasen
EP0244659A2 (de) * 1986-04-09 1987-11-11 Combustion Engineering, Inc. Mikrobiologische Entschwefelung von Gasen
FR2625918A1 (fr) * 1988-01-18 1989-07-21 Bertin & Cie Procede et installation d'epuration d'effluents gazeux contenant de l'anhydride sulfureux et eventuellement des oxydes d'azote
WO1991018661A1 (en) * 1990-06-04 1991-12-12 Abb Environmental Services Inc. Microbial removal of nitrogen oxides from gases
EP0496290A2 (de) * 1991-01-25 1992-07-29 Steag Ag Verfahren und Kraftwerksanlage zum Verwerten von Klärschlamm
EP0528110A1 (de) * 1991-08-17 1993-02-24 Degussa Aktiengesellschaft Verfahren zur biologischen Abluftreinigung
WO1995024960A1 (en) * 1994-03-16 1995-09-21 Vapo Oy Process and apparatus for the purification of gases
WO1995034371A1 (en) * 1994-06-15 1995-12-21 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Method and device for the removal of ammonia from a gas
WO1997019196A1 (en) * 1995-11-22 1997-05-29 North Carolina State University Bioreactor process for the continuous removal of organic compounds from a vapor phase process stream
WO1999059705A1 (en) * 1998-05-18 1999-11-25 Regenerative Environmental Equipment Co., Inc. Process and materials for removing pollutants
US8679230B2 (en) 2008-12-19 2014-03-25 Michael L. Strickland Reducing emissions of VOCs from low-pressure storage tanks
WO2015040100A1 (en) * 2013-09-18 2015-03-26 Yara International Asa Process and biofilter system for h2s removal from a h2s contaminated energy production gas stream containing methane and use of such a biofilter system

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102009053867A1 (de) * 2009-11-20 2011-05-26 Terranova Energy Gmbh Verfahren zur Herstellung von Bodenzusatzstoffen zur Verbesserung der Kationenaustauschkapazität, der Nährstoff- und der Wasserhaltefähigkeit von Böden

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2374070A1 (fr) * 1976-12-15 1978-07-13 Daimler Benz Ag Systeme de regulation pour une installation de lavage de gaz a regeneration de liquide de lavage
DE3227375A1 (de) * 1982-07-22 1984-03-15 Keramchemie GmbH, 5433 Siershahn Verfahren zur reinigung von biologisch abbaubare verunreinigungen enthaltende abluft

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2374070A1 (fr) * 1976-12-15 1978-07-13 Daimler Benz Ag Systeme de regulation pour une installation de lavage de gaz a regeneration de liquide de lavage
DE3227375A1 (de) * 1982-07-22 1984-03-15 Keramchemie GmbH, 5433 Siershahn Verfahren zur reinigung von biologisch abbaubare verunreinigungen enthaltende abluft

Cited By (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0218958A2 (de) * 1985-10-15 1987-04-22 Combustion Engineering, Inc. Mikrobiologische Entschwefelung von Gasen
EP0218958A3 (en) * 1985-10-15 1989-02-08 Combustion Engineering, Inc. Microbiological desulfurization of gases
EP0244659A2 (de) * 1986-04-09 1987-11-11 Combustion Engineering, Inc. Mikrobiologische Entschwefelung von Gasen
EP0244659A3 (en) * 1986-04-09 1988-04-06 Combustion Engineering, Inc. Microbiological desulfurization of gases
FR2625918A1 (fr) * 1988-01-18 1989-07-21 Bertin & Cie Procede et installation d'epuration d'effluents gazeux contenant de l'anhydride sulfureux et eventuellement des oxydes d'azote
EP0326457A1 (de) * 1988-01-18 1989-08-02 Bertin & Cie Verfahren und Anlage zur Reinigung von Schwefeloxyde und eventuell Stickoxyde enthaltenden Abgasen
WO1991018661A1 (en) * 1990-06-04 1991-12-12 Abb Environmental Services Inc. Microbial removal of nitrogen oxides from gases
EP0496290A2 (de) * 1991-01-25 1992-07-29 Steag Ag Verfahren und Kraftwerksanlage zum Verwerten von Klärschlamm
EP0496290A3 (de) * 1991-01-25 1992-08-12 Steag Ag Verfahren und Kraftwerksanlage zum Verwerten von Klärschlamm
EP0528110A1 (de) * 1991-08-17 1993-02-24 Degussa Aktiengesellschaft Verfahren zur biologischen Abluftreinigung
WO1995024960A1 (en) * 1994-03-16 1995-09-21 Vapo Oy Process and apparatus for the purification of gases
US5747331A (en) * 1994-03-16 1998-05-05 Vapo Oy Process and apparatus for the purification of gases
WO1995034371A1 (en) * 1994-06-15 1995-12-21 Nederlandse Organisatie Voor Toegepast- Natuurwetenschappelijk Onderzoek Tno Method and device for the removal of ammonia from a gas
NL9400976A (nl) * 1994-06-15 1996-01-02 Tno Werkwijze en inrichting voor het verwijderen van ammoniak uit gas.
WO1997019196A1 (en) * 1995-11-22 1997-05-29 North Carolina State University Bioreactor process for the continuous removal of organic compounds from a vapor phase process stream
US5954858A (en) * 1995-11-22 1999-09-21 North Carolina State University Bioreactor process for the continuous removal of organic compounds from a vapor phase process stream
WO1999059705A1 (en) * 1998-05-18 1999-11-25 Regenerative Environmental Equipment Co., Inc. Process and materials for removing pollutants
US6143553A (en) * 1998-05-18 2000-11-07 Regenerative Environmental Equipment Co., Inc. Process and materials for removing pollutants
US8679230B2 (en) 2008-12-19 2014-03-25 Michael L. Strickland Reducing emissions of VOCs from low-pressure storage tanks
WO2015040100A1 (en) * 2013-09-18 2015-03-26 Yara International Asa Process and biofilter system for h2s removal from a h2s contaminated energy production gas stream containing methane and use of such a biofilter system
US9890343B2 (en) 2013-09-18 2018-02-13 Yara International Asa Process and biofilter system for H2S removal from a H2S contaminated energy production gas stream containing methane and use of such a biofilter system

Also Published As

Publication number Publication date
EP0186925B1 (de) 1988-09-14
ATE37172T1 (de) 1988-09-15
DE3564935D1 (en) 1988-10-20
NL8403773A (nl) 1986-07-01

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